Squarylium compounds and optical information recording medium using the same

ABSTRACT

Squarylium compounds having the following formula (I), ##STR1## and an optical information recording medium comprising a substrate, and a recording layer formed on the substrate, comprising a squarylium compound having formula (II) are disclosed: ##STR2##

This application is a continuation-in-part of application Ser. No.07/341,325, filed Apr. 20, 1989, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to squarylium compounds which absorb nearinfrared rays, and to an optical information recording medium using thesame.

2. Discussion of Background

Materials which absorb near infrared rays have various uses, forinstance, for (i) safe-light filters for photosensitive materials whichare sensitive to infrared rays; (ii) infrared-light-cutting filters forcontrolling the growth of plants; (iii) materials for cutting heat raysof sunlight; (iv) infrared-light-cutting filters for protecting eyetissues from infrared rays; (v) infrared-light-cutting filters for lightreceiving elements of semiconductors.

In addition to the above, a recording material for use in an opticalinformation recording medium is one of important uses of thenear-infrared-rays-absorbing materials.

Hitherto, cyanine dyes such as phthalocyanine dyes; phenanthrene dyes;naphthoquinone dyes; and pyrylium dyes have been known asinfrared-absorbing materials, and optical information recording mediacomprising such dyes have also been disclosed, for example, in JapaneseLaid-open Patent Application 55-97033, 58-83344, 58-224793, 58-214162and 59-24692.

Phthalocyanine dyes, however, are disadvantageous in that they have lowphotosensitivity and high decomposition temperatures, and are notreadily vacuum-deposited. Further, since they have extremely lowsolubility in organic solvents, they cannot be coated by liquid coating.

Phenanthrene and naphthoquinone dyes are readily vacuum-deposited, butlow in reflectance. The low reflectance causes a low contrast between arecorded area and a non-recorded area when recorded by laser beams. Thiswill bring about inaccurate reproduction of recorded information.

Pyrylium and cyanine dyes are soluble in solvents, so that they can becoated by liquid coating. However, since these dyes have low lightresistance, they are readily deteriorated by the light employed for thereproduction of recorded information.

SUMMARY OF THE INVENTION

Accordingly, a first object of the present invention is to providecompounds capable of highly absorbing near infrared rays, which areeasily vacuum-deposited, and have high solubility in organic solvents,high preservation stability, high light resistance, high reflectance andhigh stability to the light employed for the reproduction of recordedinformation, and yield high C/N ratio when used in an opticalinformation recording medium.

A second object of the present invention is to provide an opticalinformation recording medium comprising such compounds, which has highreflectance, high preservation stability, high stability to the lightemployed for the reproduction of recorded information, and yields highcontrast and high C/N ratio.

The first object of the invention can be attained by squaryliumcompounds represented by the following formula (I): ##STR3## in which R¹and R² independently represent hydrogen, an alkyl group having 1 to 4carbon atoms, an aralkyl group, or an aryl group, or R¹ and R² form anaromatic, heterocyclic or alkylene ring which may have a substituent, incombination with two adjacent carbon atoms in the ring to which R¹ andR² are bonded;

R³ represents an alkyl group having 1 to 4 carbon atoms, an aralkylgroup, an aryl group or an alkoxyl group having 1 to 4 carbon atoms; nis an integer of 0 to 3, and when n is 2 or 3, R³ s may be the same ordifferent, or form an aromatic, heterocyclic or alkylene ring which mayhave a substituent, in combination with two adjacent carbon atoms in thering to which R³ s are bonded;

R⁴ and R⁵ independently represent an alkyl group having 1 to 4 carbonatoms;

R⁶ represents an alkyl group having 1 to 4 carbon atoms, an aralkylgroup or an aryl group;

R⁷ represents a halogen, an alkyl group having 1 to 4 carbon atoms, anaralkyl group, an aryl group or an alkoxyl group having 1 to 4 carbonatoms; m is an integer of 0 to 4, and when m is 2, 3 or 4, R⁷ s may bethe same or different, or form an aromatic, heterocyclic or alkylenering which may have a substituent, in combination with two adjacentcarbon atoms in the ring to which R⁷ s are bonded.

The second object of the present invention can be achieved by an opticalinformation recording medium comprising a substrate, and a recordinglayer formed on the substrate, which comprises any of the squaryliumcompounds represented by the following formula (II), when necessary,with an undercoat layer being interposed between the substrate and therecording layer and/or a protective layer being provided on therecording layer. ##STR4## in which R¹¹ and R¹² each represent hydrogen,an alkyl group having 1 to 8 carbon atoms, an aralkyl group, or an arylgroup, or R¹¹ and R¹² form an aromatic, heterocyclic or alkylene ringwhich may have a substituent, in combination with two adjacent carbonatoms in the ring to which R¹¹ and R¹² are bonded;

R¹³ represents an alkyl group having 1 to 8 carbon atoms, an aralkylgroup, an aryl group or an alkoxyl group having 1 to 8 carbon atoms; 1is an integer of 0 to 5, and when 1 is 2 to 5, R¹³ s may be the same ordifferent, or form an aromatic, heterocyclic or alkylene ring which mayhave a substituent, in combination with two adjacent carbon atoms in thering to which R¹³ s are bonded;

R¹⁴ and R¹⁵ each represent an alkyl group having 1 to 8 carbon atoms;

R¹⁶ represents an alkyl group having 1 to 8 carbon atoms, an aralkylgroup or an aryl group;

R¹⁷ represents a halogen, an alkyl group having 1 to 8 carbon atoms, anaralkyl group, an aryl group or an alkoxyl group having 1 to 8 carbonatoms; m is an integer of 0 to 4, and when m is 2, 3 or 4, R¹⁷ s may bethe same or different, or form an aromatic, heterocyclic or alkylenering which may have a substituent, in combination with two adjacentcarbon atoms in the ring to which R¹⁷ s are bonded.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings:

FIG. 1 is a spectroscopic characteristic chart of compound No. 1according to the present invention prepared in Synthesis Example 1;

FIG. 2 is a spectroscopic characteristic chart of compound No. 2according to the present invention prepared in Synthesis Example 2;

FIG. 3 is a spectroscopic characteristic chart of compound No. 3according to the present invention prepared in Synthesis Example 3;

FIG. 4 is a chart showing the reflection and absorption curves ofrecording medium No. 1 according to the present invention prepared inExample 1;

FIG. 5 is a graph showing the relationship between the reproductionnumber and the change in signals in recording medium No. 1 according tothe present invention prepared in Example 1; and

FIG. 6 is a chart showing the reflection and absorption curves ofrecording medium No. 6 according to the present invention prepared inExample 6.

DETAILED DESCRIPTION AND THE PREFERRED EMBODIMENTS

The squarylium compounds according to the present invention arerepresented by the following formula (I): ##STR5## in which

R¹ and R² independently represent hydrogen, an alkyl group having 1 to 4carbon atoms, an aralkyl group, or an aryl group, or R¹ and R² form anaromatic, heterocyclic or alkylene ring which may have a substituent, incombination with two adjacent carbon atoms in the ring to which R¹ andR² are bonded;

R³ represents an alkyl group having 1 to 4 carbon atoms, an aralkylgroup, an aryl group or an alkoxyl group having 1 to 8 carbon atoms; nis an integer of 0 to 3, and when n is 2 or 3, R³ s may be the same ordifferent, or form an aromatic, heterocyclic or alkylene ring which mayhave a substituent in combination with two adjacent carbon atoms in thering to which R³ s are bonded;

R⁴ and R⁵ independently represent an alkyl group having 1 to 4 carbonatoms;

R⁶ represents an alkyl group having 1 to 4 carbon atoms, an aralkylgroup or an aryl group;

R⁷ represents a halogen, an alkyl group having 1 to 4 carbon atoms, anaralkyl group, an aryl group or an alkoxyl group having 1 to 4 carbonatoms; m is an integer of 0 to 4, and when m is 2, 3 or 4, R⁷ s may bethe same or different, or form an aromatic, heterocyclic or alkylenering which may have a substituent, in combination with two adjacentcarbon atoms in the ring to which R⁷ s are bonded.

In the above formula (I), specific examples of the alkyl grouprepresented by R¹, R², R³, R⁴, R⁵, R⁶ or R⁷ are a methyl group, an ethylgroup, a propyl group, an isopropyl group, a n-butyl group and anisobutyl group.

The alkyl moiety of the alkoxyl group represented by R³ or R⁷ isidentical to that of the above alkyl groups, and specific examples ofthe alkoxyl group are a methoxy group, an ethoxy group, and anisopropoxy group.

The aralkyl group represented by R¹, R², R³, R⁶ or R⁷ preferablycontains 7 to 10 carbon atoms, and specific examples of the aralkylgroup are a benzyl group, a phenylethyl group and a phenylpropyl group.

Specific examples of the aryl group represented by R¹, R², R³, R⁶ or R⁷are a phenyl group and a naphthyl group.

Specific examples of the halogen represented by R⁷ are chlorine,bromine, and fluorine.

A typical example of the aromatic ring formed by R¹ and R², R³ s, or R⁷s is a benzene ring.

Specific examples of the heterocyclic ring formed by R¹ and R², R³ s orR⁷ s are heterocyclic rings which contain oxygen, nitrogen or sulfur,with the moieties formed by R¹ -R², R³ s or R⁷ s in the heterocyclicrings being --CH═CH--O--, ═CH--O--CH═, --N═CH--S--, --CH═CH--S--,═CH--S--CH═, --S--CH═CH--, and --O--CH═CH--.

Examples of the moieties formed by R¹ -R², R³ s or R⁷ s in the alkylenering formed by R¹ -R², R³ s or R⁷ s may have 3 or 4 carbon atoms, andexamples of such an alkylene ring include propylene and butylene.

Examples of the substituents of the aromatic ring, the heterocyclic ringand the alkylene ring in the formula (I) are the same halogen, alkylgroup, alkoxyl group, aralkyl group and aryl group as mentioned above.

The squarylium compounds according to the present invention can beprepared as follows:

Equimolar amounts of 3,4-dichloro-3-cyclobutene-1,2-dion and an azulenecompound are allowed to react in a solvent with application of heatthereto. After completion of the reaction, the solvent is removed fromthe mixture, and a residual is hydrolyzed. The hydrolyzate is reactedwith an equimolar amount of an indoline or indolium compound in asolvent while heating the reaction system, thereby preparing the desiredsquarylium compound. When an indolium compound is employed, the reactionis carried out in the presence of an equimolar amount of quinoline.

The scheme of the above reaction is as follows: ##STR6##

Specific examples of the squarylium compounds according to the presentinvention are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________     ##STR7##                                                                     No.                                                                              R.sup.1                                                                            R.sup.2                                                                          n R.sup.3                                                                           R.sup.3                                                                           R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          R.sup.6                                                                          m R.sup.7                                                                             R.sup.7                              __________________________________________________________________________     1 H    Me 2 5-iPr                                                                             8-Me   Me Me Me 0                                             2 H    Me 2 5-iPr                                                                             8-Me   Me Me Me 1 5-Cl                                        3 H    Me 2 5-iPr                                                                             8-Me   Me Me Me 2 5-A.sub.1 -6                                4 H    Me 2 5-iPr                                                                             8-Me   Me Me Bu 0                                             5 H    Me 2 5-iPr                                                                             8-Me   Et Et Et 0                                             6 H    Me 2 5-iPr                                                                             8-Me   Et Et Me 0                                             7 H    Me 2 5-iPr                                                                             8-Me   Me Me Bz 1 5-OCH.sub.3                                 8 H    Me 2 5-iPr                                                                             8-Me   Me Me Bz 1 5-Cl                                        9 H    Me 2 5-iPr                                                                             8-Me   Me Me Bz 2 5-A.sub.1 -6                               10 H    Et 3 4-Me                                                                              6-Me                                                                              8-Me                                                                             Me Me Me 1 5-OCH.sub.3                                11 H    Me 3 5-iPr                                                                             7-Me                                                                              8-Me                                                                             Me Me Me 0                                            12 iPr  Me 2 4-Me                                                                              8-Me   Me Me Me 0                                            13 2-A.sub.2 -3                                                                          0            Me Me Me 0                                            14 2=A.sub.3 =3                                                                          0            Me Me Me 0                                            15 H    H  2 4-A.sub.4 -5                                                                             Me Me Me 0                                            16 H    H  2 5-A.sub.4 -6                                                                             Me Me Me 0                                            17 2-A.sub.5 -3                                                                          0            Me Me Me 0                                            18 2-A.sub.6 -3                                                                          0            Me Me Me 0                                            19 2=A.sub.7 =3                                                                          0            Me Me Me 0                                            20 2-A.sub.8 -3                                                                          0            Me Me Me 0                                            21 H    H  2 4-A.sub.8 -5                                                                             Me Me Me 0                                            22 H    Me 3 5-iPr                                                                             7-Ph                                                                              8-Me                                                                             Me Me Me 0                                            23 2-A.sub.1 -3                                                                          1 6-OMe      Me Me Me 0                                            24 H    H  3 4-Ph                                                                              6-Ph                                                                              8-Me                                                                             Me Me Me 0                                            25 H    H  3 4-Me                                                                              6-OMe                                                                             8-Me                                                                             Me Me Me 0                                            26 H    H  2 4-Ph                                                                              8-Ph   Me Me Me 0                                            27 H    H  2 5-OMe                                                                             7-OMe  Me Me Me 0                                            28 Ph   Me 0            Me Me Me 0                                            29 H    Me 2 5-iPr                                                                             8-Me   Me Me Ph 0                                            30 H    Me 2 5-iPr                                                                             8-Me   Me Me Et 0                                            31 H    iPr                                                                              0            Me Me Me 0                                            32 H    Me 2 5-iPr                                                                             8-Me   Me Me iPr                                                                              0                                            33 H    iPr                                                                              0            Me Me Me 2 5-A.sub.1 -6                               34 H    iPr                                                                              0            Me Me Ph 0                                            35 H    iPr                                                                              0            Me Me Me 1 5-Cl                                       36 H    Me 0            Me Me Me 0                                            37 H    Ph 0            Me Me Me 0                                            38 H    iPr                                                                              0            Me Me Et 0                                            39 H    iPr                                                                              0            Me Me iPr                                                                              0                                            40 H    iPr                                                                              0            Me Me Me 1 5-Me                                       41 H    Me 0            Me Me Ph 0                                            42 H    Ph 0            Me Me Ph 0                                            43 H    iPr                                                                              0            Me Me Me 2 3-Cl, 5-Cl                                 44 H    iPr                                                                              0            Me Me Ph 2 5-A.sub.1 -6                               45 H    iPr                                                                              0            Me Me Me 1 5-OCH.sub.3                                46 H    iPr                                                                              0            Me Me A.sub.9                                                                          0                                            __________________________________________________________________________

In the above table, the following symbols respectively denote asfollows:

Me . . . Methyl group

Et . . . Ethyl group

iPr . . . Isopropyl group

Bu . . . Butyl group

Bz . . . Benzyl group

Ph . . . Phenyl group

A₁. . . --CH═CH--CH═CH--

A₂. . . --CH═CH--O--

A₃. . . ═CH--O--CH═

A₄. . . --O--CH═CH--

A₅. . . --N═CH--S--

A₆. . . --CH═CH--S--

A₇. . . ═CH--S--CH═

A₈. . . --S--CH═CH--

A₉. . . ##STR8##

Not only the squarylium compounds of the present invention, but also thesquarylium compounds of formula (II) are useful as recording materialsfor use in an optical information recording medium.

In the formula (II), the aryl group represented by R¹¹, R¹², R¹³, R¹⁶ orR¹⁷, the halogen represented by R¹⁷, the aromatic, heterocyclic oralkylene ring represented by R¹¹ and R¹², R¹³ s or R¹⁷ s and thesubstituents thereof are respectively the same as the aryl group, thehalogen, the aromatic, heterocyclic or alkylene ring defined in formula(I).

The optical information recording medium according to the presentinvention comprises a substrate and a recording layer formed thereoncomprising any of the squarylium compounds represented by the formula(II), and, if necessary, may further comprise an undercoat layer betweenthe substrate and the recording layer, and a protective layer on therecording layer.

A pair of the above recording media can be airtightly fabricated into anair-sandwiched structure in which both recording layers are faced eachother with an inner space therebetween, or a sandwiched structure inwhich both recording layers are faced each other with a protective layertherebetween.

Specific materials for each of the above layers of the opticalinformation recording medium according to the present invention and thenecessary properties for each layer will now be explained.

(1) Substrate

Only when recording of information and reproduction of recordedinformation are performed by application of laser beams to the side ofthe substrate, the substrate is required to be transparent to the laserbeams.

As the materials for the substrate, plastics such as polyester, acrylicresin, polyamide resin, polycarbonate resin, polyolefine resin, phenolresin, epoxy resin and polyimide resin, glass, ceramics and metals canbe employed.

On the surface of the substrate, preformats for address signals, andpregrooves serving as guide grooves may be formed, if necessary.

(2) Recording Layer

The recording layer comprises as the main component any of thesquarylium compounds represented by the formula (II). When a laser beamis applied to the recording medium, the recording layer undergoes someoptical changes. Thus, by application of a laser beam, information isrecorded in the recording medium.

Compounds Nos. 1 to 46 shown in Table 1 are preferable examples of therecording material for use in the recording layer of the recordingmedium of the present invention.

In order to improve the recording characteristics and stability of therecording layer, dyes such as polymethine dyes, phthalocyanine dyes,tetrahydrocholine dyes, dioxazine dyes, triphenothiazine dyes,phenanthrene dyes, anthraquinone (indanthrene) dyes, cyanine(merocyanine) dyes, croconium dyes, xantene dyes, triarylmethane dyes,pyrylium dyes, indophenol dyes and azulene dyes; and metals and metalliccompounds such as In, Sn, Te, Bi, Al, Se, TeO₂, SnO, As and Cd can bedispersed in the recording layer, or coated on the recording layer.

Further, polymeric materials; low molecular organic compounds, forinstance, aminium compounds, imonium compounds and diimonium compounds,and low molecular inorganic complex compounds, for instance,bisdithiodiketone complexes and bisphenyldithiol complexes, which arecapable of absorbing light having a longer wavelength than that of thelight that can be absorbed by the squarylium compounds, can beincorporated into the recording layer.

Stabilizing agents such as metal complexes and phenol compounds,dispersing agents, flame retarders, lubricants and plasticizers are alsousable in the recording layer when necessary.

The thickness of the recording layer is in the range of 100 Å to 10 μm,preferably 200 Å to 2 μm.

The recording layer can be formed on the substrate by any of knownmethods, for instance, vacuum deposition, chemical vapor deposition(CVD), sputtering, and liquid coating such as dip coating, spraycoating, spinner coating, blade coating, roller coating and curtaincoating.

(3) Undercoat Layer

An undercoat layer is formed between the substrate and the recordinglayer for the following purposes: (a) improvement of the adhesionbetween the substrate and the recording layer, (b) protection of therecording layer from water and gases, (c) improvement of thepreservation stability of the recording layer, (d) improvement of thereflectance of the recording layer, (e) protection of the substrate fromsolvents, and (f) formation of pregrooves.

For the above purpose (a), a variety of polymeric materials such asionomer resins, polyamide resins, vinyl resins, natural resins, naturalpolymeric materials, silicone and liquid rubber; and silane couplingagents can be employed.

For the purposes (b) and (c), inorganic compounds such as BiO₂, MgF₂,SiO, TiO₂, ZnO, TiN and SiN; and metals and metalloids such as Zn, Cu,S, Ni, Cr, Ge, Se, Au, Ag and Al can be used in addition to theabove-described polymeric materials.

The purpose (d) can be achieved by using metals such as Al, Ag and Te;and organic thin layers having metallic gloss such as methine dyes andxanthene dyes.

For the purposes (e) and (f), it is preferable to employ ultravioletray-setting resins, thermosetting resins or thermoplastic resins.

(4) Protective Layer

A protective layer is formed on the recording layer for the purposes of(a) protecting the recording layer from being scratched, dusted andstained, (b) improving the preservation stability of the recordinglayer, and (c) improving the reflectance of the recording layer.

In order to achieve the above purposes, all the above-describedmaterials for the undercoat layer are employable in the protectivelayer.

Stabilizing agents, dispersing agents, flame retarders, lubricants,anti-electrification agents, surface active agents and plasticizers canbe incorporated both in the undercoat layer and the protective layer, ifnecessary. Further, the squarylium compounds of the present inventioncan also be incorporated in these two layers.

The squarylium compounds having formula (II) are readilyvacuum-deposited. The compounds have high solubility in organicsolvents, so that they can be subjected to solution coating. Further,they are highly soluble in polymeric materials, and have highpreservation stability.

By using such squarylium compounds as a recording material, an opticalinformation recording medium having high reflectance, capable ofrecording images with high contrast, and having high preservation andreproduction stabilities can be produced.

Other features of this invention will become apparent in the course ofthe following description of exemplary embodiments, which are given forillustration of the invention and are not intended to be limitingthereof.

Synthesis Example 1

To a mixture of 1.0 g of 3,4-dichloro-3-cyclobutene-1,2-dion and 30 mlof dichloromethane, 1.3 g of guaiazulene was added at room temperature.After one-hour stirring, the dichloromethane was distilled away from themixture by a rotary evaporator. To the residue, 27 ml of acetic acid and7 ml of water were added, and the mixture was heated on an oil bath at100° C. for 15 hours. Thereafter, the acetic acid and the water weredistilled away from the mixture by a rotary evaporator, followed byaddition of 60 ml of n-butanol and 1.2 g of 1,3,3-trimethyl-2-methyleneindoline to the residue. The mixture was heated again on the oil bath at100° C. for 1 hour, and then the solvent and generated water wereremoved by a rotary evaporator. The residual product was purified bycolumn chromatography, so that 1.4 g of compound No. 1 according to thepresent invention represented by the following formula No. 1, having amelting point of 239° to 240° C., was obtained. ##STR9##

The results of the elementary analysis of the thus obtained compound No.1 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 82.82         6.95   3.12                                          Found      82.78         6.93   3.18                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 1 ofC₃₁ H₃₁ ; NO₂.

A spectroscopic characteristic chart of this compound is shown in FIG. 1(λ_(max) : 684 nm, logε: 5.0, solvent: CHCl₃). The chart indicates thatthis compound has a large absorption peak in a near infrared region.

SYNTHESIS EXAMPLE 2

Synthesis Example 1 was repeated except that 1.2 g of1,3,3-trimethyl-2-methylene indoline employed in Synthesis Example 1 wasreplaced with 1.5 g of 5-chloro-1,3,3-trimethyl-2-methylene indoline,whereby 1.0 g of compound No. 2 according to the present inventionrepresented by the following formula No. 2, having a melting point of250° to 51° C., was prepared. ##STR10##

The results of the elementary analysis of the thus obtained compound No.2 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 76.92         6.25   2.89                                          Found      76.85         6.17   2.93                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 2 ofC₃₁ H₃₀ ClNO₂.

A spectroscopic characteristic chart of this compound is shown in FIG. 2(λ_(max) : 690 nm, loge: 5.11, solvent: CHCl₃). The chart indicates thatthis compound has a large absorption peak in a near infrared region.

SYNTHESIS EXAMPLE 3

To a mixture of 1.3 g of 3,4-dichrolo-3-cyclobutene-1,2-dion and 30 mlof dichloromethane, 1.7 g of guaiazulene was added at room temperature.After one-hour stirring, the dichloromethane was distilled away from themixture by a rotary evaporator. To the residue, 34 ml of acetic acid and8 ml of water were added, and the mixture was heated on an oil bath at100° C. for 15 hours. Thereafter, the acetic acid and the water weredistilled away from the mixture by a rotary evaporator, followed byaddition of 80 ml of n-butanol, 30 ml of toluene, 3.0 g of1,1,2,3-tetramethyl-benz[e]-indolium iodide and 1.1 g of quinoline tothe residue. The mixture was heated again on an oil bath at 100° C. for3.5 hours, and then cooled. Insoluble materials were removed from themixture by filtration, and the filtrate was concentrated by a rotaryevaporator. The resulting product was purified by column chromatography,whereby 0.6 g of compound No. 3 according to the present inventionrepresented by the following formula No. 3, having a melting point ofmore than 165° C., was obtained. ##STR11##

The results of the elementary analysis of the thus obtained compound No.3 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 84.13         6.66   2.80                                          Found      84.15         6.69   2.70                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 3 ofC₃₅ H₃₃ NO₂.

A spectroscopic characteristic chart of this compound is shown in FIG. 3(λ_(max) : 699 nm, logε: 4.97, solvent: CHCl₃). The chart indicates thatthis compound has a large absorption peak in a near infrared region.

SYNTHESIS EXAMPLE 4

Synthesis Example 1 was repeated except that 1,3,3-trimethyl-2-methyleneindoline employed in Synthesis Example 1 was replaced with1-n-butyl-3,3-dimethyl-2-methylene indoline, whereby compound No. 4according to the present invention represented by the following formulaNo. 4 was prepared. ##STR12##

SYNTHESIS EXAMPLE 5

Synthesis Example 1 was repeated except that guaiazulene and1,3,3-trimethyl-2-methylene indoline employed in Synthesis Example 1were respectively replaced with 1-ethyl-4,6,8-trimethylazulene and5-methoxy-1,3,3- trimethyl-2-methylene indoline, whereby compound No. 10according to the present invention represented by the following formulaNo. 10 was prepared. ##STR13##

SYNTHESIS EXAMPLE 6

Synthesis Example 1 was repeated except that guaiazulene employed inSynthesis Example 1 was replaced with azuleno[2,1-b]thiophene, wherebycompound No. 20 according to the present invention represented by thefollowing formula No. 20 was prepared. ##STR14##

SYNTHESIS EXAMPLE 7

Synthesis Example 1 was repeated except that guaiazulene employed inSynthesis Example 1 was replaced with 4,6-diphenyl-8-methylazulene,whereby compound No. 24 according to the present invention representedby the following formula No. 24 was prepared. ##STR15##

SYNTHESIS EXAMPLE 8

Synthesis Example 1 was repeated except that guaiazulene employed inSynthesis Example 1 was replaced with 6-methoxy-4,8-dimethylazulene,whereby compound No. 25 according to the present invention representedby the following formula No. 25 was prepared. ##STR16##

SYNTHESIS EXAMPLE 9

Synthesis Example 1 was repeated except that 1.2 g of1,3,3-trimethyl-2-methylene indoline employed in Synthesis Example 1 wasreplaced with 1.6 g of 3,3-dimethyl-2-methylene- 1-phenyl indoline,whereby 1.2 g of compound No. 29 according to the present inventionrepresented by the following formula No. 29, having a decompositionpoint of 227° to 230° C., was prepared. ##STR17##

The results of the elementary analysis of the thus obtained compound No.29 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 84.51         6.50   2.74                                          Found      84.30         6.48   2.70                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 29of C₃₆ H₃₃ NO₂.

The spectroscopic characteristics of the compound determined by usingchloroform are as follows:

λ_(max) : 695 nm

logε: 5.1

SYNTHESIS EXAMPLE 10

Synthesis Example 1 was repeated except that 1.2 g of1,3,3-trimethyl-2-methylene indoline employed in Synthesis Example 1 wasreplaced with 1.3 g of 1-ethyl-3,3-dimethyl- 2-methylene indoline,whereby 1.5 g of compound No. 30 according to the present inventionrepresented by the following formula No. 30, having a melting point of207° to 209° C., was prepared. ##STR18##

The results of the elementary analysis of the thus obtained compound No.30 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 82.91         7.17   3.02                                          Found      82.60         7.34   2.97                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 30of C₃₂ H₃₃ NO₂.

The spectroscopic characteristics of the compound determined by usingchloroform are as follows:

λ_(max) : 682 nm

logε: 5.0

SYNTHESIS EXAMPLE 11

Synthesis Example 1 was repeated except that 1.3 g of guaiazuleneemployed in Synthesis Example 1 was replaced with 1.1 g of1-isopropylazulene, whereby 1.5 g of compound No. 31 according to thepresent invention represented by the following formula No. 31, having amelting point of 239° to 242° C., was prepared. ##STR19##

The results of the elementary analysis of the thus obtained compound No.31 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 82.63         6.46   3.32                                          Found      82.59         6.22   3.15                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 31of C₂₉ H₂₇ NO₂.

The spectroscopic characteristics of the compound determined by usingchloroform are as follows:

λ_(max) : 653 nm

logε: 5.0

SYNTHESIS EXAMPLE 12

Synthesis Example 1 was repeated except that 1.2 g of1,3,3,-trimethyl-2-methylene indoline employed in Synthesis Example 1was replaced with 1.3 g of 3,3-dimethyl-2-methylene-1-isopropylindoline, whereby 1.4 g of compound No. 32 according to the presentinvention represented by the following formula No. 32, having a meltingpoint of less than 123° C., was prepared. ##STR20##

The results of the elementary analysis of the thus obtained compound No.32 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 82.98         7.39   2.93                                          Found      82.90         7.32   2.76                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 32of C₃₃ H₃₅ NO₂.

The spectroscopic characteristics of the compound determined by usingchloroform are as follows:

λ_(max) : 683 nm

logε: 5.1

SYNTHESIS EXAMPLE 13

Synthesis Example 3 was repeated except that 1.7 g of guaiazuleneemployed in Synthesis Example 3 was replaced with 1.5 g of1-isopropylazulene, whereby 2.3 g of compound No. 33 according to thepresent invention represented by the following formula No. 33, having amelting point of 285° to 289° C., was prepared. ##STR21##

The results of the elementary analysis of the thus obtained compound No.33 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 84.05         6.20   2.97                                          Found      83.65         6.07   2.84                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 33of C₃₃ H₂₉ NO₂.

The spectroscopic characteristics of the compound determined by usingchloroform are as follows:

λ_(max) : 676 nm

logε:5.0

SYNTHESIS EXAMPLE 14

Synthesis Example 1 was repeated except that 1.3 g of guaiazulene and1.2 g of 1,3,3-trimethyl-2-methylene indoline employed in SynthesisExample 1 were respectively replaced with 1.1 g of 1-isopropylazuleneand 1.6 g of 3,3-dimethyl-2-methylene-1-phenyl indoline, whereby 1.5 gof compound No. 34 according to the present invention represented by thefollowing formula No. 34, having a decomposition point of 290° C., wasprepared. ##STR22##

The results of the elementary analysis of the thus obtained compound No.34 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 84.44         6.04   2.90                                          Found      84.32         6.11   2.89                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 34of C₃₄ H₂₉ NO₂.

The spectroscopic characteristics of the compound determined by usingchloroform are as follows:

λmax: 670 nm

logε: 5.1

SYNTHESIS EXAMPLE 15

Synthesis Example 1 was repeated except that 1.3 g of guaiazuleneemployed in Synthesis Example 1 was replaced with 1.4 g of1-phenylazulene, whereby 1.0 g of compound No. 37 according to thepresent invention represented by the following formula No. 37, having amelting point of 240° to 245° C., was prepared. ##STR23##

The results of the elementary analysis of the thus obtained compound No.37 were as follows:

    ______________________________________                                                 % C         % H    % N                                               ______________________________________                                        Calculated 84.37         5.53   3.07                                          Found      84.52         5.50   3.12                                          ______________________________________                                    

The above calculation was based on the formula for the compound No. 37of C₃₂ H₂₅ NO₂.

The spectroscopic characteristics of the compound determined by usingchloroform are as follows:

λ_(max) : 650 nm

logε: 5.0

EXAMPLE 1

On an acrylic photopolymer layer having a thickness of 50 μm formed on apolymethyl methacrylate disk having a thickness of 1.2 mm and a diameterof 130 mm, a spiral guide groove having a pitch of 1.6 μm, a depth of2000 Å and a half width of 0.4 μm was formed, whereby a substrate wasprepared. A 0.8 wt. % 1,2-dichloroethane solution of compound No. 1prepared in Synthesis Example 1 was spin-coated on the above-preparedsubstrate, and dried to form a recording layer having a thickness ofapproximately 800 Å, whereby recording medium No. 1 according to thepresent invention was prepared.

FIG. 4 shows a spectroscopic characteristic chart of the thus preparedrecording medium No. 1 obtained by applying parallel light beams to asmooth portion of the substrate of the above-prepared recording medium.The chart shows that the recording medium indicates high reflectance ina region of 780 to 830 nm, which corresponds to the wavelength range ofsemiconductor laser beams, which are currently used for optical disks.

In order to evaluate the recording characteristics of the recordingmedium, information was recorded from the substrate side by using asemiconductor laser beam having a beam diameter of 1.6 μm and awavelength of 790 nm under the conditions of a recording frequency of 5MHz, a line speed of 2.1 m/sec and a recording power of 3 mW.

By using the same semiconductor laser beam having a light intensity of0.2 mW/cm², the recorded information was reproduced by detecting thelight reflected from the recording medium. The detected light wassubjected to a spectrum analysis (scanning filter 30 kHz) to determinethe initial C/N ratio. Further, the reflectance (initial value) at aland portion of the guide groove was also determined by using the samesemiconductor laser beams. The results are shown in Table 2.

In order to evaluate the stability to the reproduction light, lighthaving a light intensity of 0.25 mW/cm² was applied to the recordingmedium, and the recorded information was reproduced 1,000,000 times byusing the same track. The change in the reflectance was converted to achange in signal. The results are shown in the graph in FIG. 5.

In addition to the above, the stability to the reproduction light wasevaluated by conducting a reproduction deterioration acceleration testin which the recording medium was exposed to tungsten light of 54,000lux for 10 hours, and then the reflectance and C/N ratio thereof weredetermined in the same manner as in the above. The results of thisacceleration test are shown in Table 2.

The preservation stability of the recording medium was evaluated bycarrying out an acceleration test in which the recording medium wasallowed to stand at 60° C. and 90% RH for 800 hours, followed bydetermination of the reflectance and the C/N ratio thereof in the samemanner as in the above. The results are shown in Table 2.

EXAMPLE 2

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with compound No. 10 prepared inSynthesis Example 5, whereby recording medium No. 2 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 3

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with compound No. 20 prepared inSynthesis Example 6, whereby recording medium No. 3 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 4

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with compound No. 24 prepared inSynthesis Example 7, whereby recording medium No. 4 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 5

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with compound No. 25 prepared inSynthesis Example 8, whereby recording medium No. 5 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 6

An injection-molded polycarbonate disk having a thickness of 1.2 mm anda diameter of 130 mm, with the same guide groove as in Example 1, formedby using a stamper capable of transferring a groove pattern identical tothe guide groove in Example 1, was spin-coated with a 1 wt. %methanol-1,2-dichloroethane-butanol solution (weight ratio=8/1.5/0.5) ofcompound No. 3 prepared in Synthesis Example 3 to form a recordinglayer, whereby recording medium No. 6 according to the present inventionwas prepared.

FIG. 6 is a spectroscopic chart of the recording medium. The recordingcharacteristics of the recording medium were evaluated in the samemanner as in Example 1. The results are shown in Table 2.

EXAMPLE 7

Example 6 was repeated except that compound No. 3 used in Example 6 asthe recording material was replaced with compound No. 2 prepared inSynthesis Example 2, whereby recording medium No. 7 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 8

Example 6 was repeated except that compound No. 3 used in Example 6 asthe recording material was replaced with compound No. 4 prepared inSynthesis Example 4, whereby recording medium No. 8 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 9

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with a mixture of compound No. 1 anda compound of the following formula (A) (weight ratio=1/1), wherebyrecording medium No. 9 according to the present invention was prepared.##STR24##

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 10

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with a mixture of compound No. 1 anda compound of the following formula (B) (weight ratio=85/15), wherebyrecording medium No. 10 according to the present invention was prepared.##STR25##

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 11

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with a formula (C) (weightratio=85/15), whereby recording medium No. 11 according to the presentinvention was prepared. ##STR26##

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 12

An injection-molded polycarbonate disk having a thickness of 1.2 mm anda diameter of 130 mm, with the same guide groove as in Example 1, formedby using a stamper capable of transferring a groove pattern identical tothe guide groove in Example 1, was coated with a 25 wt. % butanolsolution (Trademark "Colcoat N 103X" made by Colcoat Co., Ltd.), anddried for two hours to form an undercoat layer.

A 1 wt. % of methanol-1,2-dichloroethane-butanol solution (weightratio=8/1.5/0.5) of compound No. 3 prepared in Synthesis Example 3 wasspin-coated on the undercoat layer to form a recording layer, wherebyrecording medium No. 12 according to the present invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 13

On a recording medium prepared in the same manner as in Example 1,silver was vacuum-deposited under a vacuum degree of 10⁻² Torr tofurther form a protective layer, whereby recording medium No. 13according to the present invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 14

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with compound No. 31 prepared inSynthesis Example 11, whereby recording medium No. 14 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

EXAMPLE 15

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with compound No. 33 prepared inSynthesis Example 13, whereby recording medium No. 15 according to thepresent invention was prepared.

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

COMPARATIVE EXAMPLE 1

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with a compound of the followingformula (a), whereby comparative recording medium No. 1 was prepared.##STR27##

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

COMPARATIVE EXAMPLE 2

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with a compound of the followingformula (b), whereby comparative recording medium No. 2 was prepared.##STR28##

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

COMPARATIVE EXAMPLE 3

Example 1 was repeated except that compound No. 1 used in Example 1 asthe recording material was replaced with a compound of the followingformula (c), whereby comparative recording medium No. 3 was prepared.##STR29##

The recording characteristics of the recording medium were evaluated inthe same manner as in Example 1. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                         Reproduction-                                                                             Preservation                                                      Deterioration                                                                             Stability                                                         Acceleration                                                                              Acceleration                                            Initial Value                                                                           Test        Test                                             Recording        C/N           C/N         C/N                                Medium   R (%)   (dB)    R (%) (dB)  R (%) (dB)                               ______________________________________                                        No. 1    31      56      23    53    28    54                                 No. 2    31      56      21    51    26    53                                 No. 3    29      57      22    53    26    53                                 No. 4    29      57      24    54    27    54                                 No. 5    30      56      23    53    27    53                                 No. 6    26      57      16    48    25    55                                 No. 7    27      57      18    50    26    56                                 No. 8    28      56      15    48    26    55                                 No. 9    26      55      15    49    25    54                                 No. 10   29      55      27    54    26    53                                 No. 11   28      54      27    52    27    53                                 No. 12   32      57      22    53    28    54                                 No. 13   29      50      26    47    27    47                                 No. 14   36      53      31    52    29    51                                 No. 15   38      55      32    54    28    51                                 Comp.    23      55      10    --    18    49                                 No. 1                                                                         Comp.    18      54       7    --    15    43                                 No. 2                                                                         Comp.    15      53      14    53    *     *                                  No. 3                                                                         ______________________________________                                    

In the above table, "R" denotes the reflectance; "-" denotes that themeasurement was incapable; and "*" denotes that the measurement wasincapable because the recording layer was crystallized during thepreservation.

What is claimed is:
 1. An optical information recording mediumcomprising a substrate, and a recording layer formed on said substrate,which comprises a squarylium compound having formula (II): ##STR30##wherein R¹¹ and R¹² each represent hydrogen, an alkyl group having 1 to8 carbon atoms, an aralkyl group, or an aryl group, or R¹¹ and R¹² forman aromatic, heterocyclic or alkylene ring which may have a substituent,in combination with two adjacent carbon atoms in the ring to which R¹and R¹² are bonded;R¹³ represents an alkyl group having 1 to 8 carbonatoms, an aralkyl group, an aryl group or an alkoxyl group having 1 to 8carbon atoms; n is an integer of 0 to 5, and when n is 2 to 5, R¹³ s maybe the same or different, or form an aromatic, heterocyclic or alkylenering which may have a substituent, in combination with two adjacentcarbon atoms in the ring to which R¹³ s are bonded; R¹⁴ and R¹⁵ eachrepresent an alkyl group having 1 to 8 carbon atoms; R¹⁶ represents analkyl group having 1 to 8 carbon atoms, an aralkyl group or an arylgroup; R¹⁷ represents a halogen, an alkyl group having 1 to 8 carbonatoms, an aralkyl group, an aryl group or an alkoxyl group having 1 to 8carbon atoms; m is an integer of 0 to 4, and when m is 2, 3 or 4, R¹⁷ smay be the same or different, or form an aromatic, heterocyclic oralkylene ring which may have a substituent, in combination with twoadjacent carbon atoms in the ring to which R¹⁷ s are bonded.
 2. Theoptical information recording medium as claimed in claim 1, furthercomprising an undercoat layer between said substrate and said recordinglayer.
 3. The optical information recording medium as claimed in claim1, further comprising a protective layer on said recording layer.
 4. Theoptical information recording medium as claimed in claim 1, wherein thethickness of said recording layer is in the range of of 100 Å to 10 μm.